WO2021136376A1 - Matériau d'électrode négative à base de silicium et son procédé de préparation, batterie et borne - Google Patents

Matériau d'électrode négative à base de silicium et son procédé de préparation, batterie et borne Download PDF

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WO2021136376A1
WO2021136376A1 PCT/CN2020/141408 CN2020141408W WO2021136376A1 WO 2021136376 A1 WO2021136376 A1 WO 2021136376A1 CN 2020141408 W CN2020141408 W CN 2020141408W WO 2021136376 A1 WO2021136376 A1 WO 2021136376A1
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silicon
oxygen ratio
particles
low
negative electrode
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PCT/CN2020/141408
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Chinese (zh)
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雷丹
沙玉静
邓耀明
夏圣安
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华为技术有限公司
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Priority to EP20909903.5A priority Critical patent/EP4071852A4/fr
Publication of WO2021136376A1 publication Critical patent/WO2021136376A1/fr
Priority to US17/854,236 priority patent/US20220344639A1/en

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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Definitions

  • the embodiments of the present invention relate to the technical field of lithium ion batteries, in particular to silicon-based negative electrode materials and preparation methods thereof, batteries and terminals.
  • the theoretical specific capacity of silicon is 4200mAh/g, which is one of the most studied negative electrode materials that is expected to replace commercial graphite.
  • silicon will produce huge volume expansion and contraction during the charging and discharging process, which will lead to the destruction of the electrode structure and the rapid decline of battery capacity.
  • the volume expansion of silicon oxide materials is greatly reduced, but it is still very high compared to traditional graphite anodes. Therefore, it is necessary to develop a low-expansion silicon-based anode material to improve the cycle stability of the anode.
  • the embodiments of the present invention provide a silicon-based negative electrode material that has both higher capacity and lower expansion performance, so as to solve the problem of low battery cycle performance caused by excessive expansion effect of existing silicon-based materials to a certain extent.
  • the first aspect of the embodiments of the present invention provides a silicon-based negative electrode material, including a silicon-based substrate with a low silicon-oxygen ratio, and silicon-based particles with a high silicon-oxygen ratio dispersed in the silicon-based substrate with a low silicon-oxygen ratio.
  • the silicon-oxygen ratio of the low silicon-oxygen ratio silicon-based substrate is 1:x, where 1 ⁇ x ⁇ 2, and the silicon-oxygen ratio of the high silicon-oxygen ratio silicon-based particles is 1:y, where 0 ⁇ y ⁇ 1
  • the low silicon-oxygen ratio silicon-based substrate is silicon dioxide, or the low silicon-oxygen ratio silicon-based substrate includes silicon dioxide and silicon-containing crystal particles dispersed in the silicon dioxide, and the high silicon-oxygen ratio
  • the silicon-based particles are silicon particles, or the high silicon-to-oxygen ratio silicon-based particles include silicon dioxide and silicon-containing crystal particles dispersed in the silicon dioxide.
  • the low silicon-oxygen ratio silicon-based substrate is grown in situ on the surface of the high silicon-oxygen ratio silicon-based particles.
  • the silicon-containing crystal particles are crystalline silicon and/or lithium-containing silicate.
  • the particle size of the high silicon-oxygen ratio silicon-based particles is 20 nm-1000 nm.
  • the particle size of the silicon-containing crystal particles is 2 nm-15 nm.
  • the surface of the silicon-based particles with a high silicon to oxygen ratio is provided with a conductive layer and/or an ion conductive layer.
  • the material of the conductive layer is selected from one or more of conductive polymers, carbonaceous materials, metals or alloys.
  • the material of the ion conducting layer is selected from LiPO 4 , LiLaTiO 4 , Li 7 La 3 Zr 2 O 12 , LiAlO 2 , LiAlF 4 , LiAlS, Li 2 MgTiO 4 , Li 6 La 3 Zr 1.5 W One or more of 0.5 O 12.
  • the thickness of the conductive layer is 2 nm to 150 nm, and the thickness of the ion conductive layer is 2 nm to 150 nm.
  • the silicon-based negative electrode material further includes a carbon coating layer coated on the surface of the silicon-based substrate with a low silicon to oxygen ratio.
  • the particle size of the silicon-based negative electrode material is 3 ⁇ m-8 ⁇ m.
  • the silicon-based anode material provided in the first aspect of the embodiments of the present invention disperse high silicon-oxygen ratio silicon-based particles in a low silicon-oxygen ratio silicon-based substrate to achieve a limited distribution of different silicon-oxygen concentrations.
  • the high silicon-oxygen ratio silicon-based The particles can ensure that the anode material has a high lithium insertion capacity, and the low silicon-oxygen ratio silicon-based matrix with relatively small expansion effect can prevent the anode material from producing large volume changes during the lithium insertion process, and is distributed in the high silicon-oxygen
  • the silicon-based particles can effectively alleviate the volume expansion caused by the silicon-based particles with a high silicon-oxygen ratio, thereby inhibiting the crushing and pulverization of the silicon-based materials, and improving the cycle life of the silicon-based anode materials.
  • a second aspect of the embodiments of the present invention provides a method for preparing a silicon-based negative electrode material, including:
  • silicon powder and silicon dioxide powder according to the ratio of silicon to oxygen 1 : y 1 , where 0 ⁇ y 1 ⁇ 1, and then calcinate and grind to prepare silicon-based particles with high silicon to oxygen ratio; or directly use silicon particles as high silicon Oxygen than silicon-based particles;
  • the silicon powder and a silica powder by mixing a silicone ratio 1:x 1, wherein, 1 ⁇ x 1 ⁇ 2, then fired to form silicon-oxygen ratio of low vapor under vacuum or in a protective atmosphere; or separately silica powder Calcination under vacuum or protective atmosphere to form steam with low silicon to oxygen ratio;
  • the low silicon-oxygen ratio vapor is deposited on the high silicon-oxygen ratio silicon-based particles to form a low silicon-oxygen ratio silicon-based substrate to obtain a silicon-based anode material, the silicon-based anode material comprising a low silicon-oxygen ratio silicon-based substrate , And the high silicon-oxygen ratio silicon-based particles dispersed in the low silicon-oxygen ratio silicon-based substrate, the silicon-oxygen ratio of the low silicon-oxygen ratio silicon-based substrate is 1:x, where 1 ⁇ x ⁇ 2, so
  • the silicon-oxygen ratio of the high silicon-oxygen ratio silicon-based particles is 1:y, where 0 ⁇ y ⁇ 1, the low silicon-oxygen ratio silicon-based substrate is silicon dioxide, or the low silicon-oxygen ratio silicon-based substrate includes Silicon dioxide and silicon-containing crystal particles dispersed in the silicon dioxide, the high silicon-to-oxygen ratio silicon-based particles are silicon particles, or the high silicon-to-oxygen ratio silicon-based particles include silicon dioxide and are dispersed in the Silicon-containing crystal particles
  • the preparation method further includes:
  • a sol-gel method or a vapor deposition method is used to prepare a conductive layer and/or an ion conductive layer on the surface of the silicon-based particles with a high silicon to oxygen ratio.
  • the calcination in the steps of calcination and grinding to obtain silicon-based particles with a high silicon to oxygen ratio, the calcination is performed in a vacuum or a protective atmosphere, and the calcination temperature is 1100°C-1600°C.
  • the calcination temperature of the vapor with a low silicon-oxygen ratio formed by calcination in a vacuum or a protective atmosphere is 800° C.-1400° C., and the calcination time is 2-40 hours.
  • the preparation method further includes the step of preparing the high silicon-oxygen ratio silicon-based particles A lithium source is introduced during the process.
  • the preparation method further includes introducing in the process of forming a low silicon-oxygen ratio vapor Lithium source.
  • the preparation method further includes: forming a carbon coating layer on the surface of the silicon-based substrate with a low silicon to oxygen ratio.
  • the preparation method provided by the second aspect of the embodiment of the present invention has a simple process, and can obtain silicon-based anode materials with different silicon-oxygen concentration restricted distributions, so that the silicon-based anode materials have both high capacity and high cycle stability.
  • a battery includes a positive pole piece, a negative pole piece, a separator, and an electrolyte, wherein the negative pole piece includes a negative active material, and the negative active material includes the first aspect of the present invention.
  • Said silicon-based negative electrode material includes silicon-based negative electrode material.
  • the battery provided by the embodiment of the present invention has a high capacity and a better cycle performance.
  • An embodiment of the present invention also provides a terminal, including a terminal housing, a circuit board and a battery located inside the terminal housing, the battery is electrically connected to the circuit board for supplying power to the circuit board, and
  • the battery includes the battery described in the third aspect of the embodiment of the present invention.
  • FIG. 1 is a schematic structural diagram of a lithium ion secondary battery provided by an embodiment of the present invention
  • FIG. 2 is a schematic diagram of the structure of a silicon-based anode material provided by an embodiment of the present invention
  • FIG. 3 is a schematic diagram of the structure of silicon-based particles with a high silicon to oxygen ratio in an embodiment of the invention
  • Figure 4 is a schematic structural diagram of a terminal provided by an embodiment of the present invention.
  • FIG. 5 is an SEM (Scanning Electron Microscope, scanning electron microscope) diagram of a silicon-based negative electrode material provided by an embodiment of the present invention
  • 6A-6C are cross-sectional SEM (Scanning Electron Microscope, Scanning Electron Microscope) diagrams of silicon-based negative electrode materials provided by embodiments of the present invention.
  • the embodiment of the present invention provides a silicon-based negative electrode material, which can be used to make a negative electrode of a lithium ion secondary battery.
  • the core components of a lithium ion secondary battery include a positive electrode material 101, a negative electrode material 102, an electrolyte 103, a separator 104, and corresponding connecting accessories and circuits.
  • the positive electrode material 101 and the negative electrode material 102 can deintercalate lithium ions to achieve energy storage and release.
  • the electrolyte is a carrier for lithium ions to be transported between the positive and negative electrodes. The poles are separated to prevent short circuits.
  • the positive and negative electrode materials are the main part of the energy storage function, and the most direct embodiment of the energy density, cycle performance and safety performance of the battery.
  • Silicon-based anode materials have attracted attention from the industry due to their high gram capacity.
  • silicon-based negative electrode materials have the problems of large volume expansion and high surface activity, resulting in poor battery cycle performance.
  • the embodiment of the present invention provides a silicon-based negative electrode material, which has high capacity and high structural stability.
  • the silicon-based negative electrode material 10 provided by the embodiment of the present invention includes a low silicon-oxygen ratio silicon-based substrate 1 and high silicon-oxygen ratio silicon-based particles 2 dispersed in the low silicon-oxygen ratio silicon-based substrate 1.
  • the silicon-oxygen ratio of the low silicon-oxygen ratio silicon-based substrate 1 is 1:x, where 1 ⁇ x ⁇ 2, and the silicon-oxygen ratio of the high silicon-oxygen ratio silicon-based particles 2 is 1:y, where 0 ⁇ y ⁇ 1.
  • the ratio of silicon to oxygen is the molar ratio.
  • the high silicon-oxygen ratio silicon-based particles have a lithium insertion capacity of about 1500-4000mAh/g, which can ensure that the anode material has a high lithium insertion capacity, while the low silicon-oxygen ratio silicon-based substrate has a lithium insertion capacity of about 400-1500mAh. /g, which is larger than traditional graphite and amorphous carbon materials.
  • the silicon-based substrate is distributed around the silicon-based particles with a high silicon-oxygen ratio, which can effectively alleviate the volume expansion caused by the silicon-based particles with a high silicon-oxygen ratio, thereby inhibiting the crushing and pulverization of the silicon-based anode material, and improving the cycle life of the silicon-based anode material.
  • the low silicon-to-oxygen ratio silicon-based substrate 1 includes a silicon dioxide 11 substrate and silicon-containing crystal particles 12 dispersed in the silicon dioxide 11 substrate, that is, a silicon oxide system.
  • Low silicone may be a silicone ratio than that of silicon-based substrate 1 by controlling the content of silicon crystal grains 12 is controlled, in particular, silicone ratio 1:x 1, 1 ⁇ x 1 ⁇ 2.
  • the silicon-oxygen ratio of the low silicon-oxygen ratio silicon-based substrate 1 may be but not limited to 1:1.1, 1:1.2, 1:1.3, 1:1.5, 1:1.7, 1:1.8, 1:1.9 .
  • the silicon-containing crystal particles may be crystalline silicon and/or lithium-containing silicate.
  • the crystalline silicon may be monocrystalline silicon or polycrystalline silicon.
  • the silicon-containing crystal particles 12 are uniformly dispersed in the silica 11 matrix.
  • the low silicon-oxygen ratio silicon-based substrate 1 is silicon dioxide, that is, the silicon-oxygen ratio is 1:2.
  • the high silicon-to-oxygen ratio silicon-based particles 2 include a silicon dioxide 21 matrix and silicon-containing crystal particles 22 dispersed in the silicon dioxide 21 matrix, that is, a silicon oxide system.
  • the silicon-oxygen ratio of the high silicon-oxygen ratio silicon-based particles 2 can be controlled by controlling the content of the silicon-containing crystal particles 22. Specifically, the silicon-oxygen ratio is 1 :y 1 , 0 ⁇ y 1 ⁇ 1.
  • the silicon-oxygen ratio of the high silicon-oxygen ratio silicon-based particles 2 may be, for example, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, 1:0.8, 1:1.
  • the silicon-containing crystal particles may be crystalline silicon and/or lithium-containing silicate.
  • the silicon-containing crystal particles 22 are uniformly dispersed in the silica 21.
  • the high silicon-oxygen ratio silicon-based particles 2 are pure silicon particles, that is, the silicon-oxygen ratio is 1:0.
  • the pure silicon particles have a high capacity, and the pure silicon particles can be monocrystalline silicon or polycrystalline silicon.
  • the low silicon-oxygen ratio silicon-based substrate 1 is a dense structure grown in situ on the surface of the high silicon-oxygen ratio silicon-based particles 2. That is, the low silicon-to-oxygen ratio silicon-based substrate 1 and the high silicon-to-oxygen ratio silicon-based particles 2 are not traditional physical mixing and multi-interface combination.
  • the specific surface area of the silicon-based composite material is as small as possible. In the embodiment of the present invention, the specific surface area of the silicon-based negative electrode material is in the range of 0.5-5 m 2 /g.
  • the particle size of the silicon-based particles with a high silicon to oxygen ratio may be 20 nm to 1000 nm. Furthermore, the particle size of the high silicon-oxygen ratio silicon-based particles may be 20 nm-500 nm, and further, may be 50 nm-200 nm. Controlling the particle size of the high silicon-oxygen ratio silicon-based particles in a suitable range can better alleviate the volume expansion during the battery cycle, while maintaining a higher gram capacity of active materials.
  • the particle size of the silicon-containing crystal particles may be 2 nm-15 nm. Further, the particle size of the silicon-containing crystal particles may be 3 nm-10 nm. Specifically, for example, it may be 2 nm, 3 nm, 5 nm, 7 nm, 10 nm, 12 nm, or 15 nm. Silicon-containing crystal particles of suitable particle size will not cause large volume changes and stresses, and on the other hand can ensure a high degree of ion intercalation.
  • a coating layer may be provided on the surface of the silicon-based particles with a high silicon to oxygen ratio to achieve different material properties.
  • the conductive material can be coated to improve the conductivity
  • the ion conductor material can be coated to improve the ion conductivity.
  • the surface of the silicon-based particles with a high silicon to oxygen ratio is coated with a conductive layer 23.
  • the conductive material of the conductive layer may include, but is not limited to, one or more of conductive polymers, carbonaceous materials, metals, and alloys.
  • conductive polymers include, but are not limited to, polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene, polyphenylene vinylene, and polydiacetylene; carbonaceous materials include, but are not limited to, amorphous carbon, graphitic carbon, carbon fiber, Carbon nanotubes, graphene; metals include, but are not limited to, Li, Al, Mg, Ti, Cr, Mn, Co, Ni, Cu, and W metals.
  • the alloy may specifically be an alloy containing the foregoing metal elements.
  • the thickness of the conductive layer may be 2 nm to 150 nm, further, it may be 10 nm to 100 nm, and further, it may be 50 nm to 80 nm.
  • the conductive layer can increase the electrical conductivity of silicon-based particles with a high silicon-oxygen ratio, and increase the interface conductivity between silicon-containing substrates and silicon-based particles with different silicon-oxygen ratio structures; on the other hand, it can improve the conductivity of silicon-based particles with high silicon-oxygen ratio.
  • a restriction layer is formed on the surface to effectively reduce the volume expansion caused by the deintercalation of lithium.
  • the surface of the silicon-based particles with a high silicon to oxygen ratio is coated with an ion-conducting layer.
  • the ion conductor material of the ion conductive layer may include, but is not limited to, LiPO 4 , LiLaTiO 4 , Li 7 La 3 Zr 2 O 12 , LiAlO 2 , LiAlF 4 , LiAlS, Li 2 MgTiO 4 , Li 6 La 3 One or more of Zr 1.5 W 0.5 O 12.
  • the thickness of the ion-conducting layer may be 2 nm-150 nm, further, it may be 10 nm-100 nm, and further, it may be 50 nm-80 nm.
  • the ion conductive layer can effectively improve the ion conductivity between two different silicon-oxygen ratio structures in the negative electrode material.
  • the ion-conducting layer can increase the conductivity of silicon-based particles with a high silicon-oxygen ratio, and increase the interface conductivity between the silicon-containing matrix and silicon-based particles with different silicon-oxygen ratio structures; on the other hand, it can increase the conductivity of silicon-based particles with high silicon-oxygen ratio.
  • a restriction layer is formed on the surface of the particles, which effectively reduces the volume expansion caused by the deintercalation of lithium.
  • the surface of the silicon-based particles with a high silicon to oxygen ratio can also be coated with the conductive layer and the ion-conducting layer at the same time.
  • the conductive layer can be inside, the ion-conducting layer is on the outside, or the ion-conducting layer is on the inside. , The conductive layer is on the outside.
  • the silicon-based negative electrode material in order to further improve the conductivity of the material, further includes a carbon coating layer coated on the surface of the silicon-based substrate with a low silicon to oxygen ratio, and the carbon coating layer constitutes an outer shell.
  • the thickness of the carbon coating layer may be 2 nm-2000 nm, and further may be 50 nm-1000 nm.
  • the material of the carbon coating layer may be hard carbon formed by cracking a carbon source, or a mixture of hard carbon and carbon nanotubes and/or graphene embedded in it.
  • the surface carbon coating layer can effectively enhance the surface conductivity of the silicon-based composite material and improve the anti-expansion effect of the particles; at the same time, it can effectively reduce the reaction between the low silicon-oxygen ratio silicon-based substrate and the electrolyte, and reduce by-products.
  • the particle size of the silicon-based negative electrode material is 3 ⁇ m-8 ⁇ m, specifically, for example, it may be 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, or 8 ⁇ m.
  • a suitable particle size range can make the material have a suitable specific surface area without excessive consumption of electrolyte, and at the same time, it can better alleviate volume expansion.
  • the shape of the silicon-based negative electrode material is not limited, and may be a regular or irregular shape, such as a spherical shape, a quasi-spherical shape, and the like.
  • an embodiment of the present invention also provides a method for preparing a silicon-based negative electrode material, including:
  • silica powder and silicon powder by mixing a silicone ratio 1:x 1, wherein, 1 ⁇ x 1 ⁇ 2, then fired to form silicon-oxygen ratio of low vapor under vacuum or in a protective atmosphere; or separately dioxide
  • the silicon powder is calcined in a vacuum or protective atmosphere to form a vapor with a low silicon to oxygen ratio;
  • step S103 depositing the low silicon-oxygen ratio vapor obtained in step S102 on the high silicon-oxygen ratio silicon-based particles to form a low silicon-oxygen ratio silicon-based substrate to obtain a silicon-based anode material, the silicon-based anode material comprising a low silicon-oxygen ratio silicon-based substrate, And high silicon-oxygen ratio silicon-based particles dispersed in a low silicon-oxygen ratio silicon-based matrix.
  • the firing operation is performed in a vacuum or a protective atmosphere, and the firing temperature may be 1100°C to 1600°C, and further, the firing temperature may be 1200°C to 1400°C.
  • the vacuum degree of the vacuum condition may be 10 -3 -10 -1 Pa
  • the protective atmosphere may include an inert atmosphere or a reducing atmosphere, and specifically may be at least one of nitrogen, helium, argon, and hydrogen. .
  • step S101 may specifically be: the silicon powder and the silicon dioxide powder are mixed uniformly to obtain a mixture, and the mixture is heated at 1100°C to 1600°C under 10 -3 -10 -1 Pa, vacuum or protective atmosphere. Calcining and cooling to obtain a high silicon-oxygen ratio silicon oxide product; then by liquid phase ball milling or jet milling, the aforesaid product is ground to 20nm-1000nm to obtain high silicon-oxygen ratio silicon-based particles.
  • the protective atmosphere includes an inert atmosphere or a reducing atmosphere, and specifically may be at least one of nitrogen, helium, argon, and hydrogen. After the silicon powder and silicon dioxide powder are mixed, they can be uniformly mixed by ball milling.
  • step S101 further includes introducing a lithium source during the process of preparing the high silicon-oxygen ratio silicon-based particles.
  • the lithium source is specifically a lithium salt.
  • the lithium salt may be one or more of LiH, LiAlH 4 , Li 2 CO 3 , LiNO 3 , LiAc, and LiOH.
  • the introduction of the lithium source is conducive to improving the first charge and discharge efficiency of the battery.
  • step S101 may further include: preparing a conductive layer and/or an ion-conducting layer on the surface of silicon-based particles with a high silicon-to-oxygen ratio by using a sol-gel method or a vapor deposition method.
  • the conductive layer can be prepared in the following manner: Put the high silicon-to-oxygen ratio silicon-based particles obtained in step S101 into an atmosphere furnace, pass in an organic gas source such as methane, propane, acetylene, etc., and vapor-deposit at 750°C-1000°C , To obtain silicon-based particles with a high silicon to oxygen ratio covered by the conductive layer, and the thickness of the conductive layer may be 2 nm-150 nm.
  • the ion-conducting layer can be prepared in the following manner: the high silicon-oxygen ratio silicon-based particles obtained in step S101 and the ion-conducting coating material or the source material and solvent of the ion-conducting coating material and solvent are uniformly mixed and dried to obtain the mixture. Under a mild atmosphere, the mixture is treated at 600°C-1200°C for 0.5-10h to obtain high silicon-oxygen ratio silicon-based particles covered by the ion-conducting layer.
  • the thickness of the ion-conducting layer can be 2nm-150nm.
  • the calcination temperature of calcination in a vacuum or a protective atmosphere to form a low silicon-oxygen ratio vapor is 800° C.-1400° C.
  • the calcination time is 2-40 hours. Further, the calcination time is 2 hours or more, and further, it can be 6 hours or more.
  • step S102 further includes introducing a lithium source during the formation of a low silicon-to-oxygen ratio vapor.
  • the lithium source is specifically a lithium salt.
  • the lithium salt may be one or more of LiH, LiAlH 4 , Li 2 CO 3 , LiNO 3 , LiAc, and LiOH.
  • the introduction of the lithium source is conducive to improving the first charge and discharge efficiency of the battery.
  • step S103 the specific operation of depositing the low silicon-oxygen ratio vapor on the high silicon-oxygen ratio silicon-based particles to form a low silicon-oxygen ratio silicon-based substrate is as follows:
  • step S103 may further include coating a carbon coating layer on the surface of the silicon-based substrate with a low silicon to oxygen ratio.
  • gas-phase coating, liquid-phase coating or solid-phase coating methods can be used for carbon coating.
  • step S103 after the low silicon-oxygen ratio vapor deposition is completed or after a carbon coating layer is coated on the surface of the low silicon-oxygen ratio silicon-based substrate, it is further crushed and ground to obtain the desired particle size Silicon-based anode material.
  • the preparation method provided by the embodiment of the present invention has a simple process, and can obtain silicon-based negative electrode materials with different silicon-oxygen concentration restricted distributions, so that the silicon-based negative electrode materials have both high capacity and high cycle stability.
  • the embodiment of the present invention also provides a battery, including a positive pole piece, a negative pole piece, a separator, and an electrolyte, wherein the negative pole piece includes a negative active material, and the negative active material includes the negative material provided in the above embodiments of the present invention.
  • the battery may specifically be a lithium ion battery.
  • the battery provided by the embodiment of the present invention has high capacity and better cycle performance, and can be used in terminal consumer products, such as mobile phones, tablet computers, portable computers, notebook computers, and other wearable or movable electronic devices.
  • the embodiment of the present invention also provides a terminal 200.
  • the terminal 200 can be a mobile phone, a tablet computer, a notebook computer, a portable computer, a smart wearable product, and other electronic products.
  • the terminal 200 includes the terminal 200 assembled on the outside of the terminal.
  • the 201 may include a front cover assembled on the front side of the terminal and a rear case assembled on the rear side, and the battery may be fixed inside the rear case.
  • step (3) Put the product obtained in step (3) into an atmosphere furnace, pass methane, vapor deposition occurs at 750-1000°C, and form a carbon coating layer on the surface of the product to obtain a silicon-based negative electrode material.
  • FIG. 5 is an SEM image of the silicon-based negative electrode material prepared in Example 1 of the present invention. It can be seen from the figure that the particle size of the silicon-based negative electrode material is basically 3 ⁇ m-8 ⁇ m.
  • 6A is a cross-sectional SEM image of a silicon-based negative electrode material. In the figure, 1 is a silicon-based substrate with a low silicon-oxygen ratio, 2 is a silicon-based particle with a high silicon-oxygen ratio, and 3 is a carbon coating layer on the surface of a silicon-based substrate with a low silicon-oxygen ratio; 6B is an enlarged view of a silicon-based substrate with a low silicon-oxygen ratio in the area A in FIG.
  • FIG. 6A in which the dark black aggregates in the white box are silicon-containing crystal particles
  • FIG. 6C is a silicon-based particle with a high silicon-oxygen ratio in the B area in FIG. 6A
  • Figure 6B and Figure 6C show that the low silicon-to-oxygen ratio silicon-based matrix and the high silicon-to-oxygen ratio silicon-based particles are dispersed in the two silicon-containing crystal particles.
  • the difference in the composition of the silicon oxide matrix is that the distribution density and number of silicon-containing crystal particles are different, which results in a different silicon-to-oxygen ratio.
  • the single crystal silicon is ball milled to a particle size of about 200 nm, which is used as a silicon-based particle with a high silicon-to-oxygen ratio;
  • step (3) Put the product obtained in step (3) into an atmosphere furnace, pass methane, vapor deposition occurs at 750-1000°C, and form a carbon coating layer on the surface of the product to obtain a silicon-based negative electrode material.
  • the single crystal silicon is ball milled to a particle size of about 200 nm, which is used as a silicon-based particle with a high silicon-to-oxygen ratio;
  • Li 3 PO 4 coated high silicon-oxygen ratio silicon-based particles The thickness of the Li 3 PO 4 coating layer is 8-15 nm; and the high silicon-oxygen ratio silicon-based particles coated with Li 3 PO 4 are uniformly spread on the collector of the high-temperature vacuum furnace;
  • step (3) Put the product obtained in step (3) into an atmosphere furnace, pass methane, vapor deposition occurs at 750-1000°C, and form a carbon coating layer on the surface of the product to obtain a low-expansion silicon-based negative electrode material.
  • SiO 1.1 powder (silicon particles uniformly distributed in the silicon dioxide matrix) with a particle size of about 200 nm in an ethanol solution, mix uniformly, and control the solid content to about 25% to form a slurry;
  • the silicon-based negative electrode materials prepared in Example 1, Example 2, and Example 3 of the present invention and the silicon-oxygen/carbon composite material prepared in Comparative Example 1 were mixed with graphite in a certain ratio to form a gram capacity of 500mAh/ g negative material, and matched with the positive electrode material lithium cobalt oxide to prepare soft-packed batteries and test the electrochemical performance. According to the same test system, test the electrode sheet expansion of the fully charged state of the battery, and after 600 cycles of charge and discharge Measure the cell expansion, the results are shown in Table 1:
  • the battery prepared by using the silicon-based anode material of the embodiment of the present invention has significantly improved cycle performance compared with the battery prepared by the existing traditional silicon-oxygen/carbon composite anode material, and the expansion rate of the electrode sheet in the fully charged state Significantly reduced, the expansion rate of the battery cell after 600 cycles is significantly reduced.
  • the silicon-based anode material of the embodiment of the present invention realizes the limited distribution of different silicon-oxygen concentrations by dispersing the silicon-based particles with high silicon-oxygen ratio in the silicon-based substrate with low silicon-oxygen ratio, and the obtained silicon-based anode material has high capacity. And high cycle stability.
  • the high silicon-oxygen ratio silicon-based particles can ensure that the anode material has a high lithium insertion capacity, while the low silicon-oxygen ratio silicon-based substrate will not produce large volume changes during the lithium insertion process, and the low silicon-oxygen ratio silicon-based substrate Distributed around the silicon-based particles with a high silicon-oxygen ratio can effectively alleviate the volume expansion caused by the silicon-based particles with a high silicon-oxygen ratio, thereby inhibiting the crushing and pulverization of the silicon-based anode material and improving the cycle life of the silicon-based anode material.
  • a conductive layer on the surface of silicon-based particles with high silicon-to-oxygen ratio can increase the conductivity of silicon-based particles with high silicon-to-oxygen ratio, and improve the interface conductivity between silicon-containing substrate and silicon-based particles with different silicon-to-oxygen ratio structures;
  • a restriction layer is formed on the surface of silicon-based particles with a high silicon-to-oxygen ratio, which effectively reduces the volume expansion caused by the deintercalation of lithium.

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Abstract

L'invention concerne un matériau d'électrode négative à base de silicium (10) et son procédé de préparation, ainsi qu'une batterie et une borne (200) comprenant le matériau d'électrode négative à base de silicium (10). Le matériau d'électrode négative à base de silicium (10) comprend une matrice à base de silicium (1) ayant un faible rapport silicium sur oxygène et des particules à base de silicium (2) ayant un rapport silicium sur oxygène élevé dispersé dans celle-ci. Le rapport silicium sur oxygène dans la matrice à base de silicium (1) ayant un faible rapport silicium sur oxygène est de 1:x, où 1 < x ≤ 2, et le rapport silicium sur oxygène dans les particules à base de silicium (2) ayant un rapport silicium sur oxygène élevé est de 1:y, où 0 ≤ y ≤ 1. La matrice à base de silicium (1) ayant un faible rapport silicium sur oxygène est le dioxyde de silicium (11), ou comprend du dioxyde de silicium (11) et des particules cristallines contenant du silicium (12) dispersée dans le dioxyde de silicium (11) ; et les particules à base de silicium (2) ayant un rapport silicium sur oxygène élevé sont des particules de silicium, ou comprennent du dioxyde de silicium (11) et des particules de cristal contenant du silicium (12) dispersées dans le dioxyde de silicium (11). Le matériau d'électrode négative à base de silicium (10) a une capacité élevée et une faible propriété d'expansion en même temps.
PCT/CN2020/141408 2019-12-31 2020-12-30 Matériau d'électrode négative à base de silicium et son procédé de préparation, batterie et borne WO2021136376A1 (fr)

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